EP0889106B1 - Verfahren und Zusammensetzung zum Verbinden von Komponenten mit Glas - Google Patents

Verfahren und Zusammensetzung zum Verbinden von Komponenten mit Glas Download PDF

Info

Publication number
EP0889106B1
EP0889106B1 EP98118323A EP98118323A EP0889106B1 EP 0889106 B1 EP0889106 B1 EP 0889106B1 EP 98118323 A EP98118323 A EP 98118323A EP 98118323 A EP98118323 A EP 98118323A EP 0889106 B1 EP0889106 B1 EP 0889106B1
Authority
EP
European Patent Office
Prior art keywords
sheet material
acrylate
adhesive sheet
mixture
pigment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98118323A
Other languages
English (en)
French (fr)
Other versions
EP0889106A1 (de
Inventor
Michael A. c/o 3M Co. Johnson
Jon M. c/o 3M Co. Pennycook
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0889106A1 publication Critical patent/EP0889106A1/de
Application granted granted Critical
Publication of EP0889106B1 publication Critical patent/EP0889106B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/04—Joining glass to metal by means of an interlayer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/04—Joining glass to metal by means of an interlayer
    • C03C27/048—Joining glass to metal by means of an interlayer consisting of an adhesive specially adapted for that purpose
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose

Definitions

  • the invention relates to a thermosettable pressure-sensitive adhesive, a sheet material comprising the adhesive, and a method for bonding components to optically transparent substrates.
  • U.S. Patent No. 5,160,780 (Ono) describes the use of an organopolysiloxane material (also referred to in the industry as silicone rubbers) useful for bonding a mirror base to a glass plate.
  • the organopolysiloxane becomes cross-linked after autoclaving at elevated temperatures.
  • the silicone rubbers are elastomeric and can be subject to creep during sustained loads.
  • Thermosetting pressure sensitive adhesive materials have been described in U.S. Patent No. 5,086,088 (Kitano et al.). Viscoelastic materials useful in damping constructions are described in U.S. Patent No. 5,262,232 (Wilfong et al.).
  • a method of bonding a component to an optically transparent substrate comprising disposing a pressure-sensitive adhesive sheet material between said component and said optically transparent substrate so that said adhesive sheet material is adhered to said component and said substrate.
  • the adhesive sheet material comprises the photopolymerization reaction product of starting materials comprising:
  • the present invention provides colored thermosettable pressure-sensitive adhesive sheet materials which change in the shade of color on curing.
  • the preferred adhesives after thermal curing, have a relatively low elasticity and are characterized by having an elongation at break of less than 100%, and preferably less than 75%.
  • the cured adhesives have good vibration damping properties and exhibit a tan delta greater than 0.1 between a range of between about 0°C and 170°C.
  • the adhesive sheet materials are pressure-sensitive in nature, i.e., tacky, and have a storage modulus between about 5x10 4 and about 10 7 dynes per square centimeter at room temperature before thermal curing.
  • the adhesive may be cured by radiation.
  • the adhesives are thermoset and have a storage modulus greater than 2x10 7 at temperatures between -40°C and 100°C.
  • the sheet material is initially prepared by coating a photopolymerizable, thermosettable pressure sensitive adhesive composition onto a film treated with a release coating and exposing to ultraviolet radiation to form the sheet material.
  • the sheet material is subsequently adhesively adhered between two objects to be bonded, and thermally cured at temperatures from about 100°C to 200°C for about 5 to 60 minutes.
  • the pressure-sensitive adhesive is cured to form a thermoset resin, the adhesive becomes lighter in color as measured by a HunterLab colorimeter, and indicates when sufficient curing has occurred.
  • the adhesive comprises an acrylic moiety, an epoxy moiety, and a pigment.
  • the adhesive comprises an acrylic moiety, an epoxy moiety, a pigment, and an organofunctional silane.
  • the epoxy moiety comprises from about 20 to 150 parts by weight per one hundred parts of acrylate, i.e., the acrylate and the co-polymerizable monomers, and preferably from 40 to 120 parts epoxy per one hundred parts of acrylate, and more preferably 60 to 100 parts of epoxy per one hundred parts of acrylate.
  • the pigment comprises a carbon black or graphite pigment.
  • Preferred acrylic materials include photopolymerizable prepolymeric or monomeric acrylate mixtures.
  • Useful acrylic materials include monoethyleneically unsaturated monomers that have a homopolymer glass transition temperature of less than 0°C.
  • Preferred monomers are monofunctional acrylic or methacrylic esters of non-tertiary alkyl alcohols having from 2 to 20 carbon atoms, and preferably from 4 to 12 carbon atoms in the alkyl moiety.
  • Useful esters include n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, lauryl acrylate, octadecyl acrylate, and mixtures thereof.
  • the acrylate moiety includes at least one co-polymerizable reinforcing monomer.
  • the reinforcing monomer is selected to have a higher homopolymer glass transition temperature than a homopolymer of only the acrylate monomer.
  • Useful reinforcing monomers include isobornyl acrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl piperidine, N,N-dimethylacrylamide, and acrylonitrile.
  • an acidic monomer such as acrylic acid
  • the amount of acid is preferably less than about 2 percent by weight of the acrylic moiety, i.e., the total weight of the acrylate, the co-polymerizable reinforcing monomer, and the acidic monomer.
  • the acrylate will generally be present in an amount of about 50 to 95 parts by weight and the reinforcing monomer will be present in a corresponding amount of 50 to 5 parts by weight.
  • the adhesive compositions also include a free radical photoinitiator that is activatable by ultraviolet radiation.
  • a useful photoinitiator is benzil dimethyl ketal (IrgacureTM 651 available from Ciba Geigy).
  • the photoinitiator is typically used in amounts from about 0.01 to 5 parts by weight per 100 parts of the acrylate monomers.
  • the adhesives of the invention also preferably include an acrylate cross-linking agent.
  • the cross-linking agent increases the modulus of the adhesive in the pressure-sensitive state so that when it is used to bond an object to a surface with pressure either from the weight of the object or from an external source it resists flowing out and around the object during thermal curing.
  • Useful cross-linking agents are those that are free-radically polymerizable from acrylate monomers such as divinyl ethers and multi-functional acrylates that do not interfere with the curing of the epoxy resin.
  • multi-functional acrylates examples include 1,6-hexanediol diacrylate, tri-methylol-propane triacrylate, pentaerythritol tetraacrylate, and 1,2-ethylene glycol diacrylate. Amounts up to about 1 part per 100 parts acrylate monomers are preferred, and amounts of 0.01 to 0.2 part are preferred.
  • Useful epoxy resins are selected from the group of compounds that contain an average of more than one, and preferably at least two epoxy groups per molecule.
  • the epoxy resin can be either solid, semi-solid, or liquid at room temperature. Combinations of different types of epoxy resins can be used.
  • Representative epoxy resins include phenolic epoxy resins, bisphenol epoxy resins, hydrogenated epoxy resins, aliphatic epoxy resins, halogenated bisphenol epoxy resins, novolac epoxy resins, and mixtures thereof.
  • Preferred epoxy resins are those formed by the reaction of bisphenol-A with epichlorohydrin. Examples of commercially available epoxy resins include EponTM 828 and EponTM 1001 from Shell Chemical Co.
  • the epoxy resins are cured with any type of an epoxy hardener, preferably a heat activatable hardener.
  • the hardener is included in an amount sufficient to affect the curing of the epoxy under heat.
  • the hardener is selected from the group comprising dicyandiamide or polyamine salts.
  • the heat activatable hardener will typically be used in an amount of about 0.1 to 20 parts by weight, and preferably 0.5 to 10 parts by weight per 100 parts by weight of the acrylate monomers.
  • an accelerator in the adhesive composition before making the sheet material so that the resin can fully cure at a lower temperature, or within a shorter period of time.
  • Imidazoles and urea derivatives are particularly preferred as accelerators because of their ability to extend the shelf life of the sheet materials.
  • Examples of preferred imidazoles are 2,4-diamino-6-(2'-methyl-imidazoyl)-ethyl-s-triazine isocyanurate, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2'-methylimidazoyl)-ethyl-s-triazine, hexakis (imidazole)nickel phthalate, and toluene bisdimethylurea.
  • An accelerator may be used in amounts up to about 20 parts by weight per 100 parts by weight of the acrylate monomers.
  • the pigment that is selected for modifying the adhesive formulation preferably exhibits good light transmittance below 400 nm.
  • Light transmittance is pigment concentration dependent; the higher the loading of pigment, the lower the amount of light that will be capable of penetrating into the center of the adhesive mass.
  • Light transmittance may be measured using a UV-visible spectrophotometer such as Hewlett Packard HP8452A UV-visible Diode Array Spectrophotometer.
  • the amount of light transmittance below 400 nm should be measurable (i.e., >0%), especially in the region where the photoinitiator exhibits absorbance. This insures that detectable light energy is penetrating through the thickness of the adhesive mass and allows the absorption characteristics of the photoinitiator to perform its initiation function by absorbing light energy.
  • a pigment is any substance that imparts color to another substance or mixture.
  • Preferred pigments include carbon black, and graphite pigments.
  • a useful commercially available pigment is an 18% graphite dispersion in phenyloxyacrylate sold under the tradename PenncoTM 9B117 by Penncolor, Doylestown, PA. Both carbon black and graphite exhibit uniform transmittance as a function of wavelength through the visible and UV regions of the electromagnetic spectrum. They also exhibit a decrease in transmittance as pigment concentration increases.
  • the amount of pigment used should not exceed a concentration threshold that unduly interferes with achieving acceptable cure of the adhesive composition through its thickness. In practice the proper amount of pigment is influenced by the intensity of the light source and the thickness of the adhesive mass.
  • the adhesive of the invention also includes an organofunctional silane.
  • Silanes have the following general formula
  • the silanes that are useful in the practice of the present invention include those having the following organic functionalities wherein R 1 is either vinyl, halogen, epoxy, acrylate, methacrylate, amine, mercapto, styryl or ureido; and R 2 , R 3 , and R 4 is halo, methoxy, ethoxy, propoxy, or beta-methoxyethoxy; and n is an integer between 0 and 8.
  • Organofunctional silanes are commercially available from such sources as Huls, America. The silanes are incorporated in a fashion as to impart specific performance and visual characteristics to the tape construction. The incorporation of organofunctional silanes has been discovered to provide unexpected and highly beneficial properties to acrylate/epoxy hybrid adhesive compositions. Most silanes participate exclusively in either the UV or thermal curing steps. The silanes may participate in both the UV and thermal curing steps if combination of silanes is used, or if the particular silane happens to have functionalities that participate in both curing steps
  • the silanes are used in amounts sufficient to affect the desired properties.
  • the specific function of the silane is to alter the tape properties after UV cure or after the thermal curing step.
  • One such property is the modulus or stiffness of the adhesive, which can be changed from a semi-structural adhesive to a structural adhesive simply by incorporation of a silane.
  • the color shade of the tape after final curing can also be changed with the incorporation of organofunctional silanes.
  • Organosilanes can also be used to cross-link the acrylate phase through various methods.
  • One method involves allowing the individual vinyl or acrylate functional silane to condense with another identical silane molecule.
  • Another method involves incorporation of an inorganic filler such as fumed silica, glass bubbles or other inorganic fillers that are capable of condensing with the silane functionality, which creates an inorganic cross-linking scaffold. Both of these approaches accomplish the desired function of gelling the acrylate phase of the hybrid adhesive tape construction.
  • the acrylate moiety is purposefully left uncrosslinked.
  • the purpose of this is to impart thermally induced mass flow characteristics to the overall adhesive composition.
  • both the acrylate species and epoxy species are mobile and capable of flowing when exposed to the thermal curing step.
  • the advantage of this is to impart gap filling and sealing properties to the tape construction.
  • the use of vinyl or acrylate functional silanes would be avoided because of their tendency to self condense and thereby cross-link the acrylate phase. Glycidyl functional silanes would be used in this case.
  • a preferred method for manufacturing the inventive tape constructions of the present invention involves four distinct steps.
  • the first step involves the dissolving, blending, and dispersion of the epoxy resins and curatives in the acrylate monomers or syrup along with any fillers and silanes.
  • the second step involves coating the compounded formulation on a single support liner, or between two liners to a given thickness and exposing the formulation to curing radiation. Enough radiation should be used to achieve an overall nonvolatile content that is >95%, as measured by thermogravimetric analysis.
  • the third step involves converting the tape to rolls and assembly of the tape to the adherends.
  • the final step involves exposing the bonded assembly to heat which initiates the epoxy curing mechanism and results in conversion and gellation of the epoxy portion of the composition.
  • phase separation of the epoxy occurs resulting in a two-phase morphology.
  • the formation of two-phase morphology is what is believed to cause the shade change in the tape construction through a scattering mechanism.
  • the function of the silanes is to specifically adjust and tailor this phase separation, and to result in domain size in such a fashion as to achieve specific target properties in the final tape construction.
  • the discovery that silanes can radically alter the final tape appearance in pigmented systems is a simple and easy means of insuring that uniform performance in the tape product is achieved on a consistent basis.
  • additives that can be used include fibers, woven and nonwoven fabrics, glass or polymeric microspheres, and fillers such as silica.
  • organic dyes are capable of achieving a shade change during the thermal curing step, but do not demonstrate the ability to adjust the shade of the tape is attributed to the solubility of the dye in the individual phases in the tape.
  • inorganic pigments being particulate in nature are selectively excluded from the discontinuous phase during the phase separation process.
  • the function of the silane is to control the resulting morphology (i.e., domain size and distribution) which enables one to alter the distribution of pigment particles in the tape leading to a change in the final shade of the tape. This is accomplished through a simple modification in the formulation.
  • the adhesives of the invention are useful for bonding a wide range of objects to various surfaces.
  • Objects and surfaces can include glass, ceramics, metals, glass frit, plastics, and the like.
  • the adhesives are useful in bonding objects to glass plate, such as automobile windshields, or other optically transparent substrates so that the color change can be used as an indication of sufficient curing.
  • the color of the adhesive can also be modified to provide an aesthetically pleasing surface when viewed through the window.
  • the adhesives of the invention are also particularly useful in bonding non-transparent surfaces together when it is desirable to provide a particular color in the adhesive bond line.
  • Objects that may be bonded to glass substrates include mirror bases for rear view mirrors, speakers, interior lights, and the like.
  • a pressure sensitive adhesive sheet material having a pigmented thermally curable adhesive is adhered to a mirror base which is then bonded to a glass plate.
  • the composite is then heated to a temperature sufficient to cure the adhesive to a thermoset state, and to effect a visible color change.
  • the color change is noted as a decrease in the intensity of the color or an increase in the 'L' value of the color as measured with a HunterLab colorimeter. For example, a black sheet material before final curing and having an 'L' value between 10 and 15 will turn to a gray color after thermally curing with an 'L' value between 20 and 40.
  • a 1.27 cm by 15.2 cm strip of the sheet material is laminated to a 0.13 mm thick strip of anodized aluminum.
  • the aluminum strip is then laminated to a cold rolled stainless steel panel (304-BA) cleaned with 3 wipes of a 50/50 mixture of water and isopropanol and rolled down with 2 passes of a 6.8 kilogram roller.
  • the panel is then attached to a fixture in one jaw on an Instron Tester, so that the aluminum strip is pulled off at a 90° angle at a speed of 30.48 cm/minute.
  • the peel adhesion is recorded in pounds per half inch, and converted to Newtons per decimeter (N/dm).
  • the shear strength of the adhesive is determined by adhering a 1.27 cm by 2.54 cm strip of the sheet material between overlapping ends of ED-500 E-coated panels available from ACT (Advanced Coatings Technology, Hilsdale, MI), measuring 2.54 cm by 7.5 cm such that the free ends of the panels extend in opposite directions.
  • the 2.54 dimension of the sheet material is placed across the width of the panels.
  • the composite is rolled down with 2 passes of a 6.8 kg roller, then cured in an oven at 140°C for 25 minutes.
  • the sample is then cooled to room temperature and tested by extending the free ends of the panel in the jaws of an Instron Tensile Tester and separating the jaws at a speed of 5 cm/min. The results are recorded in pounds per inch and reported herein in MegaPascals (MPa).
  • the sheet material is thermally cured for 25 minutes at 177°C and cooled to room temperature.
  • a dumbbell shaped test sample (prepared according to ASTM D-412) is clamped into the jaws of on Instron Tensile Tester and the jaws are separated at a speed of 50.8 cm per minute. The tensile force required to break the test sample is shown in the tables in megaPascals (MPa). The elongation at break is reported in percent of the original length (%).
  • the color of a sample before and after curing is determined using a HunterLab colorimeter.
  • the Color 'L' value is a HunterLab scale of lightness and darkness in color in which high numbers, i.e., close to 100, are white, and low numbers, i.e., close to 0 are black.
  • the test is performed according to manufacturer's instructions on a Color 'L' 100 Colorimeter and a D25A Optical Sensor, both available from HunterLab Associates, Reston, VA.
  • the instrument is calibrated with a white tile having an 'L' value of 92, and a black tile having an ;L' value close to 0. A gray tile having an 'L' value of 30.9 is checked for comparison.
  • the pressure sensitive adhesive sheet materials are measured for 'L' values before thermal curing by removing one of the polyester films from a 152.4 cm by 152.4 cm sample, and placing the exposed adhesive surface to the sensor.
  • To cure the adhesive one of the polyester films from a 152.4 cm by 152.4 cm sample is removed and the adhesive is placed in a flat bottomed aluminum pan with the other polyester film against the pan. The adhesive in the pan is then heated at 140°C for 25 minutes, and then cooled to room temperature. The other film is removed from the adhesive, and the glossy side of the cured sheet material is measured for 'L' value.
  • the adhesives of the invention consistently exhibit an increase in the 'L' value after thermal curing, which indicate that the cured adhesives have a lighter color than the uncured sheet material.
  • This test is a measure of how well a mirror base (also referred to as a mirror button) adheres to a glass plate.
  • a U-shaped sintered stainless steel mirror button measuring 22 mm by 28 mm (obtained from SSI, Janesville, Wisconsin) is lightly sandblasted and cleaned by either wiping with acetone, or cleaning in an ultrasonic cleaner.
  • a clear, tempered glass plate measuring 12.7 cm by 5.08 cm by 0.396 cm (available from Abrisa Industrial Glass, Ventura CA) is cleaned by wiping three times with a 50/50 mixture of distilled water and isopropanol. The plate is warmed in an oven at 82°C for at least 10 minutes.
  • the mirror button is then adhered to the glass plate and laminated using a heated platen set at 177°C and pressurized by an air cylinder with a line pressure of 550 kiloPascals line pressure for 6 seconds.
  • the assembly is then heated in an oven at 140°C for 25 minutes.
  • the sample is then conditioned at room temperature and 40-60% relative humidity for at least 24 hours before testing.
  • the glass plate is then mounted vertically in a test fixture in one clamp of an Instron Tensile Tester A.
  • a 70 mm long lever arm is attached to the mirror button so that it extends horizontally.
  • the lever arm is then clamped into the Instron, and the lever arm is pulled upwardly at a rate of 2.5 millimeters per minute.
  • the maximum value at break i.e., when the mirror button breaks loose from the glass plate, is recorded in pounds and converted to Newtons.
  • a composition was prepared by mixing 29 parts n-butyl acrylate with 29 parts N-vinyl caprolactam heated to about 50°C to form a solution. The following components were added to the solution: an additional 42 parts of n-butyl acrylate, 25 parts of diglycidyl ether oligomer of bisphenol A (Epon 1001F available from Shell Chemical Co.),and 45 parts diglycidyl ether of bisphenol A (Epon 828 available from Shell Chemical Co.). The mixture was mixed with a high shear mixer for about 2 hours as the temperature increased to about 52°C.
  • the temperature was reduced to below about 38°C, and the following were added and mixed for about 30 minutes: 0.28 part benzil dimethyl ketal (Irgacure 651 available from Ciba Geigy), 0.1 part stabilizer (Irganox 1010 available from Ciba Geigy), 0.05 part hexanediol diacrylate, and 0.38 part black pigment (PenncoTM9B117).
  • 0.28 part benzil dimethyl ketal Irgacure 651 available from Ciba Geigy
  • 0.1 part stabilizer Irganox 1010 available from Ciba Geigy
  • 0.05 part hexanediol diacrylate available from Ciba Geigy
  • 0.38 part black pigment PenncoTM9B117
  • the coated composite was then irradiated on both the top and bottom of the composite with ultraviolet lamps which have 90% of the emissions between 300 and 400 nanometers (nm), and a peak emission at 351 nm as measured with a UVIRAD radiometer (Model No. VR365CH3) available from E.I.T. (Electronic Instrumentation & Technology, Inc.).
  • the intensity was about 2 milliwatts/square centimeter (mW/sq cm), and the energy above and below the coated composite was 350 milliJoules/square centimeter (mJ/sq cm), and the total energy was 700 mJ/sq cm.
  • the coated sheet was tested according to the above described test methods, and test results are shown in Table 1.
  • the adhesive sheet material was cured at 177°C for 25 minutes and the thermomechanical properties of the adhesive were determined using a Rheometrics Solids Analyzer II (RSA II), available from Rheometrics, Inc., at a frequency of 1 Hz.
  • the samples were scanned from -40°C to 120°C at step increments of 2°C and a soak time of 60 seconds.
  • the adhesive had a storage modulus greater than about 2 x 10 7 dynes/square centimeter over a range of -40°C to 100°C.
  • Sheet materials were prepared as in Example 1 except that varying amounts of two types of organofunctional silanes and a mixture of varying amounts of the silanes were added to the composition in the amounts per one hundred parts of acrylate and co-polymerizable monomers (pph) as shown in Table 1. Actual sheet thicknesses are also shown.
  • the silanes used were methacryloxy propyl trimethoxy silane (M8550 available from Huls, America) and designated MPTS in the table, and glycidoxy propyl trimethoxy silane (Dynasylan-glymo CG6720 available from Huls, America) and designated GPTS in the table, and a mixture of each of the silanes.
  • the diglycidyl ether oligomer of bisphenol A was mixed with butyl acrylate in a 2:1 ratio before adding to the composition.
  • the additional amount of butyl acrylate was adjusted to 29.5 parts so that the composition, except for the silanes and pigment, was the same as in Example 1.
  • Table 1 show that the physical properties of the adhesive sheet materials of the invention can be changed with the addition of silanes to make adhesives of different modulus.
  • the color change after thermal curing consistently went from a black color to varying shades of gray (indicated by the Color 'L' values before and after curing), which shows that the final color of the adhesive can also be modified by selecting the type and amounts of silanes.
  • Sheet materials for Examples 17-19 were prepared as in Example 1 except that the amount of black pigment was varied as shown in TABLE 2.
  • Sheet materials for Examples 20-22 were prepared as in Example 1 except that a blue pigment, cupric potassium sulfate, was used in the amounts indicated in TABLE 2.
  • Sheet materials for Examples 23-27 were prepared as in Example 9 except that a red dye (para(1,2,2-cyanoethenyl)-N,N-diethyl aniline) was used.
  • Organofunctional silanes were used in Examples 24-27 as follows: Example 24 - 0.5 pph GPTS; Example 25 - 0.05 pph MPTS; Example 26 - 0.05 pph MPTS and 1.0 pph GPTS; and Example 27 - 0.5 pph MPTS and 0.5 pph GPTS.
  • the data in TABLE 2 show that the color changes can be effected by both pigments and dyes, and the amount of change can be controlled by the amount of pigment and the use of silanes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Adhesive Tapes (AREA)
  • Glass Compositions (AREA)

Claims (10)

  1. Verfahren zum Verbinden einer Komponente mit einem optisch transparenten Substrat, umfassend das Anordnen eines flächenförmigen Materials eines Haftklebemittels zwischen der Komponente und dem optisch transparenten Substrat, so dass das flächenförmige Klebstoffmaterial an der Komponente und dem optisch transparenten Substrat haftet,
    wobei das flächenförmige Klebstoffmaterial das Photopolymerisationsumsetzungsprodukt von Ausgangsmaterialien umfasst, welche umfassen:
    (a) ein Monomerengemisch oder teilweise vorpolymerisierten Sirup, umfassend mindestens einen Acrylsäureester eines Alkylalkohols und mindestens ein copolymerisierbares Monomer;
    (b) ein Epoxydharz oder ein Gemisch von Epoxydharzen;
    (c) einen wärmeaktivierbaren Härter für das Epoxydharz oder das Gemisch von Epoxydharzen;
    (d) einen Photoinitiator; und
    (e) ein Pigment,
    wobei das flächenförmige Material bei der Härtung unter Ausbildung einer duroplastischen Klebeverbindung der Komponente zum Substrat einen detektierbaren Farbwechsel durchmacht.
  2. Verfahren nach Anspruch 1, wobei die Ausgangsmaterialien ferner ein Vernetzungsmittel umfassen.
  3. Verfahren nach Anspruch 1, wobei die Ausgangsmaterialien ferner ein organofunktionelles Silan umfassen.
  4. Verfahren nach Anspruch 1, wobei das Monomerengemisch oder der teilweise vorpolymerisierte Sirup umfassen:
    (a) etwa 50 bis etwa 95 Gewichtsteile mindestens eines Acrylsäureesters eines Alkylalkohols, ausgewählt aus Isooctylacrylat, Isononylacrylat, Decylacrylat, Dodecylacrylat, Butylacrylat, Ethylhexylacrylat, und Hexylacrylat; und
    (b) etwa 50 bis etwa 5 Gewichtsteile mindestens eines copolymerisierbaren Monomers, ausgewählt aus Isobornylacrylat, N-Vinylcaprolactam, N-Vinylpyrrolidon, N-Vinylpiperidin, N,N-Dimethylacrylamid und Acrylnitril.
  5. Verfahren nach Anspruch 1, wobei das Pigment zu einem Photopolymerisationsumsetzungsprodukt mit schwarzer oder grauer Farbe führt.
  6. Verfahren nach Anspruch 1, wobei das Pigment ein Ruß- oder Graphitpigment ist.
  7. Verfahren nach Anspruch 1, wobei die Ausgangsmaterialien etwa 25 bis 40 Gewichtsteile Epoxydharz oder eines Gemischs von Epoxydharzen umfassen.
  8. Flächenförmiges Material eines Haftklebemittels, umfassend das Photopolymerisationsumsetzungsprodukt der Ausgangsmaterialien, welche umfassen:
    (a) ein Monomerengemisch oder teilweise vorpolymerisierten Sirup, umfassend mindestens einen Acrylsäureester eines Alkylalkohols und mindestens ein copolymerisierbares Monomer;
    (b) ein Epoxydharz oder ein Gemisch von Epoxydharzen;
    (c) einen wärmeaktivierbaren Härter für das Epoxydharz oder das Gemisch von Epoxydharzen;
    (d) einen Photoinitiator;
    (e) ein Pigment, und
    (f) ein organofunktionelles Silan,
    wobei das flächenförmige Material bei der Härtung einen detektierbaren Farbwechsel durchmacht.
  9. Verfahren nach Anspruch 1, wobei das Verfahren ferner den zusätzlichen Schritt des Erwärmens des flächenförmigen Materials des Haftklebemittels umfasst, nachdem das flächenförmige Klebstoffmaterial mit der Komponente und dem optisch transparenten Substrat haftend verbunden wurde.
  10. Verfahren nach Anspruch 1, wobei das Verfahren ferner den zusätzlichen Schritt des Aussetzens des flächenförmigen Materials des Haftklebemittels einer ultravioletten Strahlung umfasst, nachdem das flächenförmige Klebstoffmaterial mit der Komponente und dem optisch transparenten Substrat haftend verbunden wurde.
EP98118323A 1995-01-13 1996-01-05 Verfahren und Zusammensetzung zum Verbinden von Komponenten mit Glas Expired - Lifetime EP0889106B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US372575 1989-06-28
US37257595A 1995-01-13 1995-01-13
EP96902092A EP0802956A2 (de) 1995-01-13 1996-01-05 Verfahren und zusammensetzung zum kleben von gegenständen auf glas

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP96902092A Division EP0802956A2 (de) 1995-01-13 1996-01-05 Verfahren und zusammensetzung zum kleben von gegenständen auf glas

Publications (2)

Publication Number Publication Date
EP0889106A1 EP0889106A1 (de) 1999-01-07
EP0889106B1 true EP0889106B1 (de) 2003-07-09

Family

ID=23468748

Family Applications (2)

Application Number Title Priority Date Filing Date
EP98118323A Expired - Lifetime EP0889106B1 (de) 1995-01-13 1996-01-05 Verfahren und Zusammensetzung zum Verbinden von Komponenten mit Glas
EP96902092A Withdrawn EP0802956A2 (de) 1995-01-13 1996-01-05 Verfahren und zusammensetzung zum kleben von gegenständen auf glas

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP96902092A Withdrawn EP0802956A2 (de) 1995-01-13 1996-01-05 Verfahren und zusammensetzung zum kleben von gegenständen auf glas

Country Status (10)

Country Link
US (1) US6348118B1 (de)
EP (2) EP0889106B1 (de)
JP (1) JP4355367B2 (de)
KR (1) KR100409064B1 (de)
AU (1) AU691083B2 (de)
BR (1) BR9606832A (de)
CA (1) CA2210189A1 (de)
DE (1) DE69629053T2 (de)
ES (1) ES2201384T3 (de)
WO (1) WO1996021704A2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013055581A1 (en) 2011-10-14 2013-04-18 3M Innovative Properties Company Primerless multilayer adhesive film for bonding glass substrates

Families Citing this family (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010028953A1 (en) * 1998-11-16 2001-10-11 3M Innovative Properties Company Adhesive compositions and methods of use
JP4636513B2 (ja) * 1996-05-30 2011-02-23 日東電工株式会社 熱硬化型感圧性接着剤とその接着シ―ト類
DE69627715T2 (de) * 1996-11-12 2004-03-04 Minnesota Mining And Manufacturing Co., St. Paul Ein thermostatoplastischer vorläufer für einen druckempfindlichen klebstoff
US6861141B2 (en) 1996-12-04 2005-03-01 Gina M. Buccellato Pavement marking article and raised pavement marker that uses pressure sensitive adhesive
AU2428897A (en) * 1996-12-04 1998-06-29 Minnesota Mining And Manufacturing Company Pavement marking article
US6133335A (en) 1998-12-31 2000-10-17 3M Innovative Properties Company Photo-polymerizable compositions and articles made therefrom
US6265459B1 (en) 1998-12-31 2001-07-24 3M Innovative Properties Company Accelerators useful for energy polymerizable compositions
AU4458000A (en) 1999-12-20 2001-07-03 3M Innovative Properties Company Acidic polymer-based thermosettable psas, methods of their use, and thermoset adhesives therefrom
US6635689B1 (en) 2000-06-26 2003-10-21 3M Innovative Properties Company Accelerators for cationic polymerization catalyzed by iron-based catalysts
JP3627011B2 (ja) 2001-02-13 2005-03-09 インターナショナル・ビジネス・マシーンズ・コーポレーション 接合方法
DE10121556A1 (de) 2001-05-03 2002-11-14 Infineon Technologies Ag Verfahren zum Rückseitenschleifen von Wafern
ES2290105T3 (es) 2001-06-01 2008-02-16 Pilkington Italia S.P.A. Cristal para ventana de un elemento fijado por adherencia.
US6765037B2 (en) * 2001-11-03 2004-07-20 Dymax Corporation Photopolymerizable epoxy composition
US20030149124A1 (en) * 2001-11-27 2003-08-07 Thommes Glen A. Radiation curable resin composition for making colored three dimensional objects
WO2003048067A1 (en) * 2001-11-29 2003-06-12 Dow Global Technologies Inc. Method of bonding a window to a substrate without a primer
US6915938B2 (en) * 2002-12-04 2005-07-12 General Electric Company Method and apparatus for reducing component vibration during inertia welding
US8535473B2 (en) * 2005-03-03 2013-09-17 3M Innovative Properties Company Thermosettable adhesive tape, articles and methods
DE102005027404A1 (de) * 2005-06-13 2006-12-14 Schröders, Theo Brandschutzglas und Verfahren zu dessen Herstellung
US7781493B2 (en) 2005-06-20 2010-08-24 Dow Global Technologies Inc. Protective coating for window glass
US7786183B2 (en) * 2005-06-20 2010-08-31 Dow Global Technologies Inc. Coated glass articles
DE102005042245A1 (de) * 2005-09-05 2007-03-08 Henniges Automotive Gmbh & Co. Kg Verfahren zur Verbindung einer Fahrzeugscheibe mit einem vorgefertigten Bauteil
KR20080014269A (ko) * 2006-08-10 2008-02-14 강남케미컬 (주) 알루미늄 포일형 고광택시트
JP5295527B2 (ja) * 2007-07-18 2013-09-18 協立化学産業株式会社 積層構造体の製造方法及びそれに使用する接着剤
WO2009079647A1 (en) 2007-12-18 2009-06-25 Dow Global Technologies Inc. Protective coating for window glass having enhanced adhesion to glass bonding adhesives
KR20130129222A (ko) * 2010-11-23 2013-11-27 어드헤시브즈 리서치, 인코포레이티드 반응성 전도성 감압성 접착 테이프
DE102012222056A1 (de) * 2012-12-03 2014-06-05 Tesa Se Lamination starrer Substrate mit dünnen Klebebändern
US9994706B2 (en) * 2013-09-10 2018-06-12 Dow Global Technologies Llc Internal mold release agent for reinforced composite
KR102245276B1 (ko) * 2014-07-08 2021-04-26 엘지디스플레이 주식회사 유기 발광 표시 장치 봉지용 접착 수지 및 이를 이용한 유기 발광 표시 장치의 제조 방법
JP6220103B1 (ja) * 2014-09-23 2017-10-25 スリーエム イノベイティブ プロパティズ カンパニー 構造体接合組成物及び取付用ブラケット、並びに光起電力ソーラーモジュールにおけるそれらの使用
KR102469861B1 (ko) * 2015-04-13 2022-11-23 모멘티브 퍼포먼스 머티리얼즈 인크. 메르캅토-관능 규소화합물을 포함하는 반응성 조성물
US9630381B2 (en) 2015-05-12 2017-04-25 Whirlpool Corporation Insulation system for a cooking appliance incorporating a plurality of microsphere sheets
WO2016196561A1 (en) 2015-06-04 2016-12-08 3M Innovative Properties Company Methods of bonding hardware to vehicular glass
EP3334597A1 (de) * 2015-08-11 2018-06-20 Arcons Limited Designartikel und verfahren zur herstellung davon
WO2017053334A1 (en) * 2015-09-23 2017-03-30 3M Innovative Properties Company Structural bonding compositions and attachment brackets, and their use in photovoltaic solar modules
CN108472786B (zh) 2015-12-30 2021-07-27 3M创新有限公司 磨料制品
US10759023B2 (en) 2015-12-30 2020-09-01 3M Innovative Properties Company Abrasive articles and related methods
CN108473822B (zh) * 2015-12-30 2021-11-12 3M创新有限公司 双阶段结构粘结粘合剂
CN106189904A (zh) * 2016-07-21 2016-12-07 苏州泰仑电子材料有限公司 耐酸型丙烯酸酯压敏胶保护膜
DE102016220237A1 (de) 2016-10-17 2018-04-19 Tesa Se Verfahren zur Herstellung einer versiegelten Falzverbindung
KR102210938B1 (ko) * 2017-11-28 2021-02-01 주식회사 엘지화학 부착력이 우수한 도파관 엣지 차광용 조성물
CN111479890B (zh) 2017-12-14 2022-06-17 艾利丹尼森公司 具有宽的阻尼温度和频率范围的压敏粘合剂
JP2019119799A (ja) * 2018-01-04 2019-07-22 スリーエム イノベイティブ プロパティズ カンパニー テープ状接着剤
DE102018213824A1 (de) 2018-08-16 2020-02-20 Tesa Se Verfahren zur Herstellung einer versiegelten Falzverbindung
JP2022513629A (ja) * 2018-11-29 2022-02-09 コーニング インコーポレイテッド ガラスカバーシートのフレームへの接着
EP3894502A1 (de) * 2018-12-11 2021-10-20 Lohmann GmbH & Co. KG Wickel- und stanzbarer klebender film
JP2021195384A (ja) * 2020-06-09 2021-12-27 積水化学工業株式会社 接着剤組成物、光学部品、電子部品、及び、電子モジュール
DE102022113506A1 (de) 2022-05-30 2023-11-30 Tesa Se Verfahren zum Verbinden, Ablösen und Wiederverbinden von Substraten

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3131251A (en) * 1958-06-09 1964-04-28 Libbey Owens Ford Glass Co Mirror mounting assembly
US3285802A (en) * 1962-03-01 1966-11-15 Owens Illinois Inc Glass aerosol bottles and method for making same
GB1552046A (en) * 1977-02-02 1979-09-05 Ciba Geigy Ag Film adhesives
DE2731100C3 (de) 1977-07-09 1980-11-20 Vereinigte Glaswerke Gmbh, 5100 Aachen Verfahren zum Verkleben von Metallteilen mit Glasoberflächen, insbesondere zum Verkleben von Halteelementen für einen Rückspiegel und einer Windschutzscheibe
FR2403364A1 (fr) * 1977-09-16 1979-04-13 Commissariat Energie Atomique Materiau composite a base de fibres presentant un haut module de traction
US4483951A (en) * 1979-06-06 1984-11-20 The Standard Products Company Radiation curable adhesive compositions and composite structures
DD227861A3 (de) * 1983-01-31 1985-09-25 Zeiss Jena Veb Carl Verfahren zur herstellung von klebstoffen
DE3516661A1 (de) * 1984-05-16 1985-11-21 Merck Patent Gmbh, 6100 Darmstadt Strahlungshaertbare kleber
JPS60260666A (ja) * 1984-05-16 1985-12-23 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング 照射硬化性接着剤
WO1989005782A1 (en) 1987-12-24 1989-06-29 Asahi Glass Company Ltd. Structure and method for fitting mirror base to glass sheet surface
US5086088A (en) * 1989-03-09 1992-02-04 Minnesota Mining And Manufacturing Company Epoxy-acrylate blend pressure-sensitive thermosetting adhesives
US5587236A (en) 1991-10-09 1996-12-24 Donnelly Corporation Interior rear view mirror mounting system utilizing one-package structural adhesive
US5262232A (en) 1992-01-22 1993-11-16 Minnesota Mining And Manufacturing Company Vibration damping constructions using acrylate-containing damping materials

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013055581A1 (en) 2011-10-14 2013-04-18 3M Innovative Properties Company Primerless multilayer adhesive film for bonding glass substrates

Also Published As

Publication number Publication date
AU4653596A (en) 1996-07-31
EP0889106A1 (de) 1999-01-07
JP4355367B2 (ja) 2009-10-28
KR19980701347A (ko) 1998-05-15
EP0802956A2 (de) 1997-10-29
MX9704979A (es) 1997-10-31
ES2201384T3 (es) 2004-03-16
WO1996021704A2 (en) 1996-07-18
CA2210189A1 (en) 1996-07-18
DE69629053T2 (de) 2004-04-22
DE69629053D1 (de) 2003-08-14
US6348118B1 (en) 2002-02-19
KR100409064B1 (ko) 2005-06-02
WO1996021704A3 (en) 1996-08-22
AU691083B2 (en) 1998-05-07
JPH11502542A (ja) 1999-03-02
BR9606832A (pt) 1997-12-30

Similar Documents

Publication Publication Date Title
EP0889106B1 (de) Verfahren und Zusammensetzung zum Verbinden von Komponenten mit Glas
EP0993496B1 (de) Klebstoffzusammensetzungen beständig gegen hohe feuchtigkeit
US20190193384A1 (en) Thermosettable adhesive taped articles
EP0386909B1 (de) Druckempfindliche, thermohärtende Klebstoffe aus einer Epoxid-acrylester-Mischung
KR100344074B1 (ko) 토포그래피특성의부여방법
KR20010085543A (ko) 감압성 접착 시이트, 및 기능성 필름의 고정방법
JPH09505095A (ja) 熱硬化性感圧接着剤
KR100364042B1 (ko) 팽창성다층재료
MXPA97002286A (en) Expandable material of multip layers
JPH08508216A (ja) 形態学的シート材料及び方法
MXPA97004979A (en) Method and composition to join vid components
JP2017535233A (ja) 構造体接合組成物及び取付用ブラケット、並びに光起電力ソーラーモジュールにおけるそれらの使用
EP3353819A1 (de) Strukturverbindungszusammensetzungen und befestigungsklammern und deren verwendung in fotovoltaischen solarmodulen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AC Divisional application: reference to earlier application

Ref document number: 802956

Country of ref document: EP

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT

RIN1 Information on inventor provided before grant (corrected)

Inventor name: PENNYCOOK, JON M. C/O 3M CO.

Inventor name: JOHNSON, MICHAEL A. C/O 3M CO.

17P Request for examination filed

Effective date: 19990702

17Q First examination report despatched

Effective date: 20010926

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AC Divisional application: reference to earlier application

Ref document number: 0802956

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Designated state(s): DE ES FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69629053

Country of ref document: DE

Date of ref document: 20030814

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2201384

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040414

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1018794

Country of ref document: HK

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20080128

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20080129

Year of fee payment: 13

Ref country code: GB

Payment date: 20080129

Year of fee payment: 13

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090105

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20090119

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090105

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090107

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090105

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20141231

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69629053

Country of ref document: DE